Diazo dyes containing a hydroxy alkoxybenzene middle component and a pyrazole coupling component

ABSTRACT

The invention relates to azo dyes of the formula  (* CHEMICAL STRUCTURE *) (1) in which R, R1 and R2, independently of one another, are hydrogen, substituted or unsubstituted C1-C8alkyl or phenyl, R3 is hydrogen or substituted or unsubstituted C1-C8alkyl, C5-C7cycloalkyl or phenyl and the benzene rings I and II may be further substituted. The azo dyes are suitable for the dyeing or printing of natural or synthetic polyamide fibre materials, in particular in combination with other dyes and in particular from short liquors. The azo dyes are distinguished by generally good properties, in particular good affinity.

The present invention relates to novel azo dyes, processes for theirpreparation and the use of these dyes for the dyeing and printing offibre materials, in particular textile fibre materials.

The present invention relates to azo dyes of the formula ##STR2## inwhich R, R₁ and R₂, independently of one another, are hydrogen,substituted or unsubstituted C₁ -C₈ alkyl or phenyl, R₃ is hydrogen orsubstituted or unsubstituted C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl or phenyland the benzene rings I and II may be further substituted.

The azo dyes of the formula (1) in which R₁ and R₂ have meanings whichare different from one another and in addition R₃ is not hydrogen areusually present as a mixture of isomeric compounds of the formulae##STR3##

The designation azo dyes of the formula (1) is understood here andhereinafter also to include the abovementioned mixtures of isomers.

Examples of R, R₁, R₂ and R₃ in formula (1) as C₁ -C₈ alkyl are,independently of one another, methyl, ethyl, propyl, isopropyl, butyl,isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl or octyl, and thecorresponding radicals which are substituted, for example, by hydroxyl,C₁ -C₄ alkoxy, cyano or halogen. R as substituted C₁ -C₈ alkyl is inparticular hydroxyl-substituted C₁ -C₈ alkyl.

Examples of R₃ in formula (1) as C₅ -C₇ cycloalkyl are unsubstitutedcyclohexyl or cyclohexyl substituted by C₁ -C₄ alkyl, for example methylor ethyl.

Examples of R, R₁, R₂ and R₃ in formula (1) as phenyl are unsubstitutedphenyl or phenyl substituted by C₁ -C₄ alkyl, for example methyl orethyl, C₁ -C₄ alkoxy, for example methoxy or ethoxy, C₂ -C₄alkanoylamino, for example acetylamino or propionylamino, hydroxyl,sulfo or halogen, for example fluorine, chlorine or bromine.

Examples of substituents of benzene rings I and II are, independently ofone another, C₁ -C₄ alkyl, for example methyl or ethyl, C₁ -C₄ alkoxy,for example methoxy or ethoxy, C₂ -C₄ alkanoylamino, for exampleacetylamino or propionylamino, hydroxyl, sulfo, nitro, halogen, forexample fluorine, chlorine or bromine, sulfamoyl or sulfamoyl which ismono- or disubstituted on the nitrogen atom by C₁ -C₄ alkyl, phenyl ornaphthyl and can be further substituted in the C₁ -C₄ alkyl, phenyl andnaphthyl radical by the abovementioned substituents. Preferredsubstituents of the benzene rings I and II are C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₂ -C₄ alkanoylamino and halogen, in particular methyl, methoxy,acetylamino and chlorine.

Preferably, the azo dyes of the formula (1) contain only one sulfogroup.

Preference is given to azo dyes of the formula (1) in which R ishydrogen or unsubstituted or hydroxyl-substituted C₁ -C₄ alkyl, inparticular in which R is methyl, hydroxymethyl or ethyl, preferablymethyl or ethyl.

Further preference is given to azo dyes of the formula (1) in which R₁and R₂, independently of one another, are hydrogen, C₁ -C₄ alkyl, inparticular methyl or ethyl, or phenyl.

Furthermore, preference is given to azo dyes of the formula (1) in whichR₃ is hydrogen, C₁ -C₄ alkyl or phenyl.

In the azo dyes of the formula (1), the sulfo group is preferably boundto the benzene ring I.

Particular preference is given to azo dyes of the formula (1) in which Ris hydrogen or unsubstituted or hydroxyl-substituted C₁ -C₄ alkyl, R₁and R₂, independently of one another, are hydrogen or C₁ -C₄ alkyl, R₃is hydrogen, C₁ -C₄ alkyl or phenyl, the benzene rings I and II,independently of one another, may be further substituted by C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino or halogen and the sulfogroup is bound to the benzene ring I.

Very particular preference is given to azo dyes of the formula ##STR4##in which R is methyl or ethyl, R₁ and R₂, independently of one another,are methyl or ethyl, R₃ is hydrogen, methyl, ethyl or phenyl and thebenzene rings I and II, independently of one another, may be furthersubstituted by methyl, methoxy, acetylamino or chlorine.

The invention furthermore relates to a process for the preparation ofthe azo dyes of the formula (1), which comprises diazotising an amine ofthe formula ##STR5## in which R is as defined in formula (1) and thebenzene rings I and II may be further substituted, and coupling theresulting product onto a coupling component of the formula ##STR6## inwhich R₁ and R₂, independently of one another, are substituted orunsubstituted C₁ -C₈ alkyl or phenyl, or onto a coupling component ofthe formula ##STR7## in which R' has the meanings given for R₁ and R₂ informula (1), and reacting the reaction product of the formula ##STR8##with a hydrazine of the formula

    H.sub.2 N--NH--R.sub.3                                     ( 7),

in which R₃ is as defined in formula (1), the amine of the formula (4),the reacted coupling component of the formula (5a) or (5b) and thehydrazine of the formula (7) together containing at least one sulfogroup. Accordingly, if the amine of the formula (4) or the reactedcoupling component of the formula (5a) or (5b) contains a sulfo group,the reaction product of the formula (6) also contains such a group.

Diazotisation of the amine of the formula (4) is usually carried out byreaction with nitrous acid in aqueous mineral acid solution at lowtemperature, while coupling onto the coupling component of the formula(5a) or (5b) takes place at acidic, neutral to weakly alkaline pHvalues, in particular at a pH of 2 to 6.

The reaction of the compound of the formula (6) with a hydrazine of theformula (7) is carried out in water, an organic solvent, for examplemethanol, ethanol, pyridine or glacial acetic acid, or a mixture ofwater and an organic solvent, for example water/glacial acetic acid, ata temperature of 40° to 100° C., in particular at a temperature of 40°to 60° C.

The amines of the formula (4), the coupling components of the formula(5a) and (5b) and the hydrazines of the formula (7) are known per se orcan be prepared in analogy to known compounds.

Examples of amines of the formula (4) are

3-(β-hydroxypropoxy)-4-aminoazobenzene-2'-, -3'- or -4'-sulfonic acid,

3-(β-hydroxypropoxy)-4-amino-6-methylazobenzene-2'-, -3'- or-4'-sulfonic acid,

3-(β-hydroxypropoxy)-4-amino-6-methoxyazobenzene-2', -3'- or-4'-sulfonic acid,

3-(β-hydroxypropoxy)-4-amino-6-acetylaminoazobenzene-2'-, -3'- or-4'-sulfonic acid,

3-(β-hydroxypropoxy)-4-amino-6-chloroazobenzene-2'-, -3'- or-4'-sulfonic acid,

3-(β-hydroxypropoxy)-4-amino-2'-chloroazobenzene-3'-, -4'-, -5'- or-6'-sulfonic acid,

3-(β-hydroxybutoxy)-4-aminoazobenzene-2'-, 3'- or -4'-sulfonic acid,

3-(β-hydroxybutoxy)-4-amino-6-methylazobenzene-2'-, -3'- or -4'-sulfonicacid,

3-(β-hydroxybutoxy)-4-amino-6-methoxyazobenzene-2'-, -3'- or-4'-sulfonic acid,

3-(β-hydroxybutoxy)-4-amino-6-acetylaminoazobenzene-2'-, -3'- or-4'-sulfonic acid,

3-(β-hydroxybutoxy)-4-amino-6-chloroazobenzene-2'-, -3'- or -4'-sulfonicacid,

3-(β-hydroxybutoxy)-4-amino-2'-chloroazobenzene-3'-, -4'-, -5'- or-6'-sulfonic acid.

Examples of coupling components of the formulae (5a) and (5b) are3-diethylaminopropen-1-al, 4-diethylaminobuten-2-one, 2,4-pentanedione,2,4-hexanedione, 3,5-heptanedione, 2,4-heptanedione, 3,5-octanedione,4,6-octanedione, dibenzoylmethane, formylacetophenone andbenzoylacetone.

Examples of compounds of the formula (7) are hydrazine, methyl-, ethyl-,propyl-, isopropyl-, butyl-, isobutyl-, sec-butyl-, tert-butyl-, phenyl-and cyclohexylhydrazine and 4-sulfophenylhydrazine.

Preferred embodiments of the process according to the invention arethose in which

an amine of the formula (4) is used in which the benzene rings I and II,independently of one another, may be further substituted by C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino or halogen;

an amine of the formula (4) is used in which the sulfo group is bound tothe benzene ring I;

an amine of the formula (4) is used in which R is hydrogen orunsubstituted or hydroxyl-substituted C₁ -C₄ alkyl, in particular inwhich R is methyl, hydroxymethyl or ethyl, preferably methyl or ethyl;

a coupling component of the formula (5a) is used in which R₁ and R₂,independently of one another, are phenyl or C₁ -C₄ alkyl, in particularmethyl or ethyl, or a coupling component of the formula (5b) is used inwhich R' is hydrogen, phenyl or C₁ -C₄ alkyl, in particular methyl orethyl;

a compound of the formula (7) is used in which R₃ is hydrogen, C₁ -C₄alkyl or phenyl;

an amine of the formula (4), a coupling component of the formula (5a) or(5b) and a compound of the formula (7) are used which together containonly one sulfo group.

In a particularly preferred embodiment of the process according to theinvention, an amine of the formula (4) in which R is hydrogen orunsubstituted or hydroxyl-substituted C₁ -C₄ alkyl and the benzene ringsI and II, independently of one another, may be further substituted by C₁-C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino or halogen and the sulfogroup is bound to the benzene ring I, is diazotised, the product iscoupled onto a coupling component of the formula (5a), in which R₁ andR₂ are C₁ -C₄ alkyl, or onto a coupling component of the formula (5b),in which R' is hydrogen, and the reaction product obtained is reactedwith a compound of the formula (7), in which R₃ is hydrogen, C₁ -C₄alkyl or phenyl.

In a very particularly preferred embodiment of the process according tothe invention for the preparation of the azo dyes of the formula (1), anamine of the formula ##STR9## in which R is as defined in formula (3)and the benzene rings I and II may be substituted as indicated informula (3), is diazotised, the product is coupled onto a couplingcomponent of the formula (5a), in which R₁ and R₂ are as defined informula (3), and the reaction product obtained is reacted with acompound of the formula (7), in which R₃ is as defined in formula (3).

The invention furthermore relates to a process for the trichromaticdyeing or printing of natural and synthetic polyamide fibre materialsusing a dye mixture comprising at least one yellow- or orange-dyeing dyeof the formula (1) together with at least one red-dyeing dye and atleast one blue-dyeing dye, the dye of the formula (1) having inparticular the abovementioned preferences; preferably, the yellow- ororange-dyeing dye used is a dye of the formula (3).

In the process according to the invention for the trichromatic dyeing orprinting, at least one dye of the formula (1) is preferably usedtogether with at least one of the red-dyeing dyes of the formulae (9),(10) and (11): ##STR10## in which R₄ is substituted or unsubstituted C₁-C₈ alkyl, halogen, phenylsulfonyl or phenoxysulfonyl which isunsubstituted or substituted in the phenyl ring by C₁ -C₄ alkyl, or iscyclohexyloxycarbonylamino, C₂ -C₄ alkanoylamino, benzoylamino which isunsubstituted or substituted in the phenyl ring by halogen, or is1-azacycloheptane-N-sulfonyl or ##STR11## in which R₇ is C₁ -C₈ alkyl orunsubstituted or C₁ -C₄ alkyl-substituted phenyl or cyclohexyl and R₈ ishydrogen or C₁ -C₈ alkyl, R₅ is hydrogen, halogen, C₁ -C₈ alkyl or C₂-C₄ alkanoylamino and R₆ is hydrogen or halogen, ##STR12## in which D issubstituted or unsubstituted phenyl, thiophenyl or benzothiazolyl, R₉ isC₁ -C₈ alkyl, R₁₀ is substituted or unsubstituted C₁ -C₈ alkyl and R₁₁is hydrogen or C₁ -C₄ alkyl, and ##STR13## in which R₁₂ is C₁ -C₄ alkyl,and together with at least one blue-dyeing dye of the formula ##STR14##in which one Y is hydrogen or methyl and the other Y is C₂₋₄alkanoylamino or C₂ -C₄ hydroxyalkylsulfamoyl and Z₄ is hydrogen ormethyl, the dye of the formula (1) having in particular theabovementioned preferences; preferably, the yellow- or orange-dyeing dyeused is a dye of the formula (3).

The dyes of the formulae (9), (10), (11) and (12) used in the processaccording to the invention for the trichromatic dyeing or printing areknown per se or can be prepared in analogy to known dyes.

Examples of R₄, R₅, R₇ and R₈ in formula (9) and R₉ and R₁₀ in formula(10) as C₁ -C₈ alkyl are, independently of one another, methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl,hexyl, heptyl and octyl. R₄, R₅, R₇, R₈, R₉ and R₁₀ are preferably C₁-C₄ alkyl.

The radical R₄ in formula (9) as C₁ -C₈ alkyl can be substituted, forexample, by halogen, for example chlorine or bromine and in particularfluorine. One example is the trifluoromethyl radical.

The radical R₁₀ in formula (10) as C₁ -C₈ alkyl can be substituted, forexample, by sulfo, sulfato or phenyl. Examples are benzyl, β-sulfoethyl,γ-sulfopropyl and β-sulfatoethyl.

Examples of R₄, R₅ and R₆ in formula (9) as halogen are, independentlyof one another, fluorine, bromine or in particular chlorine.

The radical R₄ in formula (9) as benzoylamino can be substituted in thephenyl ring by halogen, for example fluorine, bromine or in particularchlorine.

The radical R₇ as phenyl or cyclohexyl and the radical R₄ asphenylsulfonyl or phenoxysulfonyl can be substituted by C₁ -C₄ alkyl,for example methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,tert-butyl or isobutyl, in particular methyl.

Examples of R₁₁ in formula (10) and R₁₂ in formula (11) as C₁ -C₄ alkylare, independently of one another, methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, tert-butyl or isobutyl, in particular methyl.

Examples of R₄ and R₅ in formula (9) and Y in formula (12) as C₂ -C₄alkanoylamino are, independently of one another, acetylamino,propionylamino or butyrylamino.

The radical D in formula (10) can be substituted, for example, byhalogen, such as fluorine, chlorine or bromine, C₁ -C₄ alkyl, such asmethyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl orisobutyl, C₁ -C₄ alkoxy, for example methoxy, ethoxy, propoxy or butoxy,C₁ -C₄ alkoxycarbonyl, for example methoxycarbonyl or ethoxycarbonyl,sulfo or C₁ -C₄ alkylaminosulfonyl which is unsubstituted or substitutedin the alkyl moiety by sulfo, for example, methylaminosulfonyl,ethylaminosulfonyl or β-sulfoethylaminosulfonyl.

Examples of Y in formula (12) as C₂₋₄ hydroxyalkylsulfamoyl radical areβ-hydroxyethylsulfamoyl, β-hydroxypropylsulfamoyl,γ-hydroxypropylsulfamoyl or β-hydroxybutylsulfamoyl.

For the process according to the invention for the trichromatic dyeingor printing, at least one of the red-dyeing dyes of the formulae (9),(10) and (11) is preferably used, R₄ in the dye of the formula (9) beingtrifluoromethyl, chlorine, acetylamino, --SO₂ N(n--C₄ H₉)₂,phenoxysulfonyl, phenylsulfonyl, 1-azacycloheptane-N-sulfonyl,cyclohexyloxycarbonylamino, benzoylamino which is unsubstituted orsubstituted in the phenyl ring by chlorine or phenylaminosulfonyl whichis unsubstituted or substituted in the phenyl ring by methyl,cyclohexylaminosulfonyl, N-(C₁ -C₂ alkyl)phenyl- or N-(C₁ -C₂alkyl)cyclohexylaminosulfonyl, R₅ being hydrogen, methyl, chlorine oracetylamino and R₆ being hydrogen or chlorine, and D in the dye of theformula (10) being phenyl which is substituted by chlorine, sulfo,methylaminosulfonyl, ethylaminosulfonyl or β-sulfoethylaminosulfonyl,thiophenyl which is substituted by methyl, methoxy- or ethoxycarbonyl orbenzothiophenyl which is unsubstituted or substituted by methyl, methoxyor sulfo, R₉ being ethyl, R₁₀ being ethyl, β-sulfatoethyl, --(CH₂)₂₋₃SO₃ H or benzyl and R₁₁ being hydrogen or methyl, and R₁₂ in the dye ofthe formula (11) being methyl.

Particularly preferably, at least one of the red-dyeing dyes of theformulae ##STR15## is used.

Also particularly preferably, at least one of the blue-dyeing dyes ofthe formulae ##STR16## is used for the process according to theinvention.

When mixtures of blue-dyeing dyes are used for the process according tothe invention, the mixture of blue-dyeing dyes of the formula (16) or(17) with a dye of the formula (18), (19) or (20) is preferred. Veryparticular preference is given to the mixture of the blue-dyeing dyes ofthe formulae ##STR17## in which Y₂ is a C₂₋₄ hydroxyalkylsulfamoylradical, and ##STR18## in which the radical --NH--CO--CH₂ CH₃ is boundin the 3 or 4 position.

For the process according to the invention for the trichromatic dyeingor printing, at least one dye of the formula (1) is very particularlypreferably used together with at least one of the red-dyeing dyes of theformulae (13), (14) and (15), in particular (13) and (14), and at leastone of the blue-dyeing dyes of the formulae (16), (17), (18), (19) and(20), the dye of the formula (1) having in particular the abovementionedpreferences; preferably, the yellow- or orange-dyeing used is a dye ofthe formula (3).

In an extremely important embodiment of the process according to theinvention for the trichromatic dyeing or printing, at least one dye ofthe formula (1) is used together with a red-dyeing dye of the formula(14) and a blue-dyeing dye of the formula (16), the dye of the formula(1) having in particular the abovementioned preferences; preferably, theyellow- or orange-dyeing dye used is a dye of the formula (3).

When dye mixtures are used in the process according to the invention,they can be prepared by mixing the individual dyes. This mixing processtakes place, for example, in suitable mills, for example ball andpinned-disc mills, and in kneaders or mixers.

Furthermore, the dye mixtures of the dyes can be prepared byspray-drying of the aqueous dye mixtures.

The dyes according to the invention of the formula (1) and the dyes usedin the process according to the invention for the trichromatic dyeing orprinting are present either in the form of their free sulfonic acid orpreferably as salts thereof.

Examples of suitable salts are the alkali metal salts, alkaline earthmetal salts or ammonium salts or the salts of an organic amine. Examplesare the sodium salts, lithium salts, potassium salts or ammonium saltsor the salt of mono-, di- or triethanolamine.

The dyes according to the invention of the formula (1) and the dyes usedin the process according to the invention usually contain furtheradditives, for example common salt or dextrin.

The process according to the invention for the trichromatic dyeing orprinting can be applied to the customary dyeing or printing processes.The dye liquors or printing pastes can, in addition to water and thedyes, contain further additives, for example wetting agents, antifoams,levelling agents or agents affecting the property of the textilematerial, for example softeners, additives for flameproof finish orsoil-, water- and oil-repellent agents and water softeners and naturalor synthetic thickening agents, for example alginates and celluloseethers.

The dyes according to the invention of the formula (1) and the processaccording to the invention for trichromatic dyeing or printing aresuitable in particular for the dyeing from short liquors, for example incontinuous dyeing processes or batchwise and continuous foam dyeingprocesses.

The dyes according to the invention of the formula (1) and the dyes usedin the process according to the invention are distinguished intrichromatic dyeing or printing by uniform colour buildup, goodaffinity, good constancy of shade even in different concentrations, goodfastness properties and in particular very good compatibility.

The dyes according to the invention of the formula (1) and the processaccording to the invention for trichromatic dyeing or printing aresuitable for the dyeing or printing not only of natural polyamide fibrematerials, for example wool, but in particular also of syntheticpolyamide fibre materials, for example nylon 6 or nylon 6.6, and aresuitable for the dyeing or printing of wool and synthetic polyamideblended fabrics or yarns.

The textile material mentioned can be present in a wide range ofprocessing forms, for example as fibre, yarn, woven fabric or knittedfabric and in particular in the form of carpets.

The azo dyes according to the invention of the formula (1) produce leveldyeings having good general fastness properties, in particular good rub,wet, wetrub and light fastness. Furthermore, the dyes according to theinvention are readily water-soluble and resistant to hard water.

In the examples which follow, parts are by weight. Temperatures aredegrees centigrade. Parts by weight relate to parts by volume as thegram relates to the cubic centimeter.

EXAMPLE 1

A neutral, hot solution of 50° of 37 parts of3-(β-hydroxypropoxy)-4-aminoazobenzene-3'-sulfonic acid in 500 parts ofwater are run simultaneously with 26 parts of an aqueous sodium nitritesolution (4N) into the mixture of 28 parts of concentrated hydrochloricacid in 200 parts of water, and the temperature of the reaction mixtureis maintained at 20° to 25° by addition of ice. After addition iscomplete, stirring is continued for 2 hours, and the nitrite excess isdestroyed with a small amount of sulfamic acid. The diazotisationmixture thus prepared is slowly run into a cold solution of 0° to 5° of14 parts of 2,4-pentanedione and 180 parts of sodium acetate in 500parts of water. After stirring at 0° to 5° for several hours, themixture is heated to 30° in order to complete the reaction, and the pHis brought to 5.5 with sodium acetate. The precipitate is then filteredoff with suction and dried at 60°, giving 44 parts of an orange powder.

5 parts of the reaction product prepared by the above procedure aresuspended in 80 parts of glacial acetic acid and 6 parts of water atroom temperature. 1.2 parts of hydrazine hydrate are added all at oncewith stirring. The reaction mixture is slowly heated to 50° and stirredfor 2 hours. Finally, it is heated at 90° for about 10 minutes until nomore educt can be detected by thin-layer chromatography. After coolingto room temperature, the dye is precipitated by addition of hydrochloricacid (2N). Filtration, washing with a small amount of water and dryingat a temperature of 80° give 4.8 parts of a dye which, in the form ofthe free acid, corresponds to the compound of the formula ##STR19##

The dye of the formula (101) dyes synthetic and natural polyamide fibrematerial in yellow hues.

EXAMPLES 2 TO 117

The procedure described in Example 1 is repeated, except that anequimolar amount of the compound of the formula ##STR20## in which thesulfo group is bound to the benzene ring I in the position given inTable 1 in column 2, R has the meanings given in Table 1 in column 3,and the benzene rings I and II do not contain any further substituents,is used instead of 37 parts of3-(β-hydroxypropoxy)-4-aminoazobenzene-3'-sulfonic acid, and anequimolar amount of the compound of the formula ##STR21## in which R₁and R₂ have the meanings given in Table 1 in columns 4 and 5 but are nothydrogen, is used instead of 14 parts of 2,4-pentanedione, and anequimolar amount of the compound of the formula

    H.sub.2 N--NH--R.sub.3                                     (7),

in which R₃ has the meanings given in Table 1 in column 6, is usedinstead of 1.2 parts of hydrazine hydrate, giving analogous dyes whichdye synthetic and natural polyamide fibre materials in yellow hues.

The dyes listed in Table 1 below, in which at least one of the radicalsR₁ and R₂ is hydrogen, are obtained as described, except that anequimolar amount of the compound of the formula ##STR22## in which R'has the meanings given for R₁ or R₂ in Table 1 and the other radical R₁or R₂ in Table 1 is hydrogen, is used instead of the compound of theformula (5a).

The dyes listed in the examples of Table 1 below, in which R₁ and R₂have meanings which are different from one another and R₃ is nothydrogem, are obtained as mixtures of isomeric compounds of the formulae##STR23## in which R, R₁, R₂ and R₃ have the meanings given in Table 1in columns 3 to 6 and the sulfo group is bound to the benzene ring I inthe position given in Table 1 in column 2, and the benzene rings I andII do not contain any further substituents. The mixtures of isomers dyesynthetic and natural polyamide fibre materials in yellow hues.

                  TABLE 1                                                         ______________________________________                                              Substituent                                                                   benzene                                                                 Ex.   ring I    R        R.sub.1                                                                             R.sub.2                                                                             R.sub.3                                  ______________________________________                                         2    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                       3    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                                4    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                         5    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                    6    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                       7    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                                8    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                         9    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   10    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                      11    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               12    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub. 3                                                                         --C.sub.2 H.sub.5                        13    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   14    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      15    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               16    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        17    4-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   18    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      19    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               20    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        21    3-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   22    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      23    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               24    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        25    2-SO.sub.3 H                                                                            --H      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   26    4-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      27    4-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               28    4-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        29    4-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   30    3-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      31    3-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               32    3-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        33    3-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   34    2-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      35    2-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   -- C.sub.2 H.sub.5                                                                  --CH.sub.3                               36    2-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        37    2-SO.sub.3 H                                                                            --H      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   38    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                      39    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               40    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                        41    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   42    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               43    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                        44    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   45    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                      46    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               47    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                        48    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   49    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      50    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               51    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        52    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   53    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      54    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               55    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        56    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   57    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      58    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub. 5                                                                  --CH.sub.3                               59    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        60    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   61    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      62    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               63    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        64    4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   65    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      66    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               67    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        68    3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub. 5                                                                  Phenyl                                   69    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      70    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               71    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        72    2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   73    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                      74    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               75    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                        76    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   77    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                      78    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               79    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          -- CH.sub.3                                                                         --C.sub.2 H.sub.5                        80    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   81    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --H                                      82    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --CH.sub.3                               83    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          --C.sub.2 H.sub.5                        84    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --CH.sub.3                                                                          Phenyl                                   85    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      86    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               87    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        88    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   89    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      90    3-SO.sub.3 H                                                                            --C.sub.2 H.sub. 5                                                                     --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               91    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        92    3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   93    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --H                                      94    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --CH.sub.3                               95    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        96    2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --CH.sub.3                                                                          --C.sub.2 H.sub.5                                                                   Phenyl                                   97    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      98    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               99    4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        100   4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   101   3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      102   3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               103   3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        104   3-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   105   2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --H                                      106   2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --CH.sub.3                               107   2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                        108   2-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --C.sub.2 H.sub.5                                                                   --C.sub.2 H.sub.5                                                                   Phenyl                                   109   4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                     n-C.sub.3 H.sub.7                                                             110   4-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                     iso-C.sub.3 H.sub.7                                                           111   3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                     n-C.sub.4 H.sub.9                                                             112   3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                     sec-C.sub.4 H.sub.9                                                           113   2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                     tert-C.sub.4 H.sub.9                                                          114   2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --CH.sub.3                                     cyclo-C.sub.6 H.sub.11                                                        115   4-SO.sub.3 H                                                                            --C.sub.2 H.sub.5                                                                      --H   --CH.sub.3                                                                          --H                                      116   2-SO.sub.3 H                                                                            --CH.sub.3                                                                             --CH.sub.3                                                                          --H   --C.sub.2 H.sub.5                        117   3-SO.sub.3 H                                                                            --CH.sub.3                                                                             --H   --H   Phenyl                                   ______________________________________                                    

EXAMPLES 118 TO 125

The procedure described in Example 1 is repeated, except that ifdesired, an equimolar amount of one of the amines listed in Table 2below in column 2 in the form of the free acid is used instead of 37parts of 3-(β-hydroxypropoxy)-4-aminoazobenzene-3'-sulfonic acid, ifdesired, an equimolar amount of a coupling component of the formula(5a), in which R₁ and R₂ are as defined in columns 3 and 4, is usedinstead of 14 parts of 2,4-pentanedione, and, if desired, an equimolaramount of the compound of the formula (7), in which R₃ is as defined incolumn 5, is used instead of 1.2 parts of hydrazine hydrate, givinganalogous dyes which dye synthetic and natural polyamide fibre materialsin golden-yellow or orange hues.

                                      TABLE 2                                     __________________________________________________________________________    Ex.                                                                              Amine                        R.sub.1                                                                           R.sub.2                                                                           R.sub.3                               __________________________________________________________________________    118                                                                               ##STR24##                   CH.sub.3                                                                          CH.sub.3                                                                          H                                     119                                                                               ##STR25##                   CH.sub.3                                                                          CH.sub.3                                                                          H                                     120                                                                               ##STR26##                   CH.sub.3                                                                          CH.sub.3                                                                          C.sub.2 H.sub.5                       121                                                                               ##STR27##                   CH.sub.3                                                                          CH.sub.3                                                                          H                                     122                                                                               ##STR28##                   CH.sub.3                                                                          CH.sub.3                                                                          H                                     123                                                                               ##STR29##                   C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                   H                                     124                                                                               ##STR30##                   C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                   H                                     125                                                                               ##STR31##                   C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                   H                                     __________________________________________________________________________

DYEING EXAMPLE 1

10 parts of nylon 6.6 fibre material (Helanca knitted fabric) are dyedin 500 parts of an aqueous liquor which contains 2 g/l of ammoniumacetate and is brought to a pH of 5 with acetic acid. The dyes used are0.05% of the red dye which, in the form of the free acid, has theformula ##STR32## 0.18% of the yellow dye which, in the form of the freeacid, has the formula (101) and 0.17% of the blue dye which, in the formof the free acid, has the formula ##STR33## the amounts given beingbased on the fibre weight.

The dyeing time at a temperature of 98° is 30 to 90 minutes. The dyedpolyamide fibre material is then removed from the liquor and rinsed anddried as usual, giving a piece of fabric which has been dyed completelylevelly in a brown hue and does not have any material-related barriness.

DYEING EXAMPLE 2

10 parts of nylon 6.6 yarn are dyed in 400 parts of an aqueous liquorwhich contains 1.5 g/l of ammonium acetate and is brought to a pH of 5.5with acetic acid. The dyes used are 0.13% of the yellow dye obtainedaccording to Example 65, 0.1% of the dye of the formula (102) and 0.12%of the dye of the formula (103), the amounts given being based on thefibre weight. The dye bath is heated to 98° C. over a period of 30minutes and maintained at 96° to 98° for 60 minutes. The dyed yarn isthen removed and rinsed and dried as usual, giving a yarn dyed in abrown hue.

DYEING EXAMPLE 3

10 parts of nylon 6.6 carpet yarn are dyed in 400 parts of an aqueousliquor which contains 1.5 g/l of ammonium acetate and is brought to a pHof 5.5 with acetic acid. The dyes used are 0.15% of the red dye of theformula ##STR34## 0.625% of the yellow dye obtained according to Example119 and 0.52% of the blue dye of the formula (103), the amounts givenbeing based on the fibre weight. The dye bath is heated to 98° over aperiod of 30 minutes and maintained at 96° to 98° for 60 minutes. Thedyed yarn is then removed and rinsed and dried as usual, giving a yarndyed in a brown hue.

DYEING EXAMPLE 4

The procedure described in Dyeing Example 3 is repeated, except that0.32% of the dye of the formula (102) and 0.61% of the dye of theformula (103) are used instead of the dyes of the formulae (104) and(103), likewise giving a yarn dyed in a brown hue.

DYEING EXAMPLE 5: (CARPET PRINTING)

A nylon 6 velour carpet having a pile weight of 400 g/m² is padded, forground shade, with an aqueous padding liquor of the followingcomposition

0.1 g/l of the dye of the formula (101),

0.1 g/l of the dye of the formula (103),

2 g/l of a thickener based on natural polysaccharides,

0.5 g/l of a wetting agent based on a sulfated alkylarylpolyglycolate,and

0.5 g/l of an antifoam based on high-boiling alcohols,

which has been brought to a pH of 4.5 with acetic acid, and squeezed offto a liquor pickup of 80%. A pattern is applied to the carpet thuspretreated via a printing screen using the following aqueous printingpaste:

1 g/l of the dye of the formula (101),

20 g/l of the dye of the formula (102),

10 g/l of the dye of the formula (103),

15 g/l of a thickener based on natural polysaccharides,

2 g/l of a wetting agent based on a sulfated alkylarylpolyglycolate,

1 g/l of an antifoam based on high-boiling alcohols.

The printing paste has been brought to a pH of 4.5 with acetic acid.

The printed material is then treated with saturated steam at 101° for 5minutes in order to fix the dyes, rinsed, neutralised, rinsed again anddried.

This gives a velour carpet having a bordeaux-coloured pattern on a paleolive ground shade having very sharp contours, good penetration and nofrosting whatsoever.

DYEING EXAMPLE 6: (CONTINUOUS CARPET DYEING)

2.7 parts of the yellow dye of the formula (101), 1.2 parts of the reddye of the formula (102) and 1.3 parts of the blue dye of the formula(103) are dissolved in 100 parts of water by boiling for a short time.This solution is then added to a solution containing 3 parts of athickener based on carbob seed flour, 5.0 parts of a coacervate-formingpadding auxiliary based on a condensation product of ahigh-molecular-weight fatty acid with a hydroxyalkylamine, 2.0 parts ofcrystalline monosodium phosphate and 1.0 part of crystalline disodiumphosphate in 500 parts of cold water. The mixture is then made up to1000 parts with cold water. 300%, relative to the carpet weight, of thisliquor having a pH of 5.5 to 6.5 are applied to an untreated nylon 6.6needle-pile carpet at a carpet rate of 8 meters per minute. Theimpregnated carpet enters a loop steamer, where it is treated withsaturated steam at 98° to 100° for 10 minutes.

After washing in a broad washing machine, a carpet dyed in a neutralbrown hue is obtained.

What is claimed is:
 1. An azo dye of the formula ##STR35## in which R, R₁ and R₂, independently of one another, are hydrogen, substituted or unsubstituted C₁ -C₈ alkyl or phenyl, R₃ is hydrogen or substituted or unsubstituted C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl or phenyl and the benzene rings I and II may be further substituted.
 2. An azo dye according to claim 1, wherein R is hydrogen or unsubstituted or hydroxyl-substituted C₁ -C₄ alkyl.
 3. An azo dye according to claim 1, wherein R₁ and R₂, independently of one another, are hydrogen, phenyl or C₁ -C₄ alkyl.
 4. An azo dye according to claim 1, wherein R₃ is hydrogen, C₁ -C₄ alkyl or phenyl.
 5. An azo dye according to claim 1, wherein the benzene rings I and II, independently of one another, may be further substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino or halogen.
 6. An azo dye according to claim 1, wherein the sulfo group is bound to the benzene ring I.
 7. An azo dye according to claim 1, wherein R is hydrogen or unsubstituted or hydroxyl-substituted C₁ -C₄ alkyl, R₁ and R₂, independently of one another, are hydrogen or C₁ -C₄ alkyl, R₃ is hydrogen, C₁ -C₄ alkyl or phenyl, the benzene rings I and II, independently of one another, may be further substituted by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino or halogen, and the sulfo group is bound to the benzene ring I.
 8. An azo dye according to claim 1 of the formula ##STR36## in which R is methyl or ethyl, R₁ and R₂, independently of one another, are methyl or ethyl, R₃ is hydrogen, methyl, ethyl or phenyl and the benzene rings I and II, independently of one another, may be further substituted by methyl, methoxy, acetylamino or chlorine.
 9. An azo dye according to claim 2, wherein R₁ and R₂ is methyl or ethyl.
 10. An azo dye according to claim 3, wherein R is methyl or ethyl.
 11. A process for the trichromatic dyeing or printing of natural and synthetic polyamide fibre materials using dye mixtures, which comprises applying to a polyamide fibre material at least one yellow- or orange-dyeing dye of the formula ##STR37## in which R, R₁ and R₂, independently of one another, are hydrogen, substituted or unsubstituted C₁ -C₈ alkyl or phenyl, R₃ is hydrogen or substituted or unsubstituted C₁ -C₈ alkyl, C₅ -C₇ cycloalkyl or phenyl, and the benzene rings I and II may be further substituted, together with at least one red-dyeing dye and at least one blue-dyeing dye.
 12. A process according to claim 11 for the trichromatic dyeing or printing, which comprises applying to a polyamide fibre material at least one of the red-dyeing dyes of the formulae (9), (10) and (11): ##STR38## in which R₄ is substituted or unsubstituted C₁ -C₈ alkyl, halogen, phenylsulfonyl or phenoxysulfonyl which is unsubstituted or substituted in the phenyl ring by C₁ -C₄ alkyl, or is cyclohexyloxycarbonylamino, C₂ -C₄ alkanoylamino, benzoylamino which is unsubstituted or substituted in the phenyl ring by halogen, or is 1-azacycloheptane-N-sulfonyl or ##STR39## in which R₇ is C₁ -C₈ alkyl or unsubstituted or C₁ -C₄ -alkyl-substituted phenyl or cyclohexyl and R₈ is hydrogen or C₁ -C₈ alkyl, R₅ is hydrogen, halogen, C₁ -C₈ alkyl or C₂ -C₄ alkanoylamino and R₆ is hydrogen or halogen, ##STR40## in which D is substituted or unsubstituted phenyl, thiophenyl or benzothiazolyl, R₉ is C₁ -C₈ alkyl, R₁₀ is substituted or unsubstituted C₁ -C₈ alkyl and R₁₁ is hydrogen or C₁ -C₄ alkyl, and ##STR41## in which R₁₂ is C₁ -C₄ alkyl, together with at least one blue-dyeing dye of the formula ##STR42## in which one Y is hydrogen or methyl and the other Y is C₂₋₄ alkanoylamino or C₂ -C₄ hydroxyalkylsulfamoyl, and Z₄ is hydrogen or methyl.
 13. A process according to claim 11 for trichromatic dyeing or printing, which comprises applying to a polyamide fibre material at least one of the red-dyeing dyes of the formulae ##STR43## together with at least one of the blue-dyeing dyes of the formulae ##STR44##
 14. A polyamide fibre material dyed or printed by the process according to claim
 11. 15. A polyamide fibre material according to claim 14, wherein said fibre material is a polyamide carpet. 